Unsaturated organo-tin mercaptide stabilizers for halo-vinyl polymers

ABSTRACT

Unsaturated organo-tin mercaptides, useful as stabilisers for halogenated vinyl resins, are obtained by reacting x mols of a mercaptocarboxylic acid HSXCOOH with y1 mols of an alcohol HOYOH or mixture thereof with y2 mols of alcohol HOY&#39;&#39;OH and/or y3 mols of alcohol ROH, where X is C1-4 alkylene or phenylene, Y is C1-10 alkylene or cycloaliphatic of 5 or 6 ring carbons, each with ethylenic and/or acetylenic bonds but not more than 2 of each type of bonds, Y&#39;&#39; is C1-10 alkylene or cycloalkylene with 5 or 6 ring carbons, R is C1-8 alkyl or alkenyl, cycloalkyl or cycloalkenyl with 5 or 6 ring carbons, or phenyl (C1-4) alkyl, with x, y1, y2 and y3 having specified inter-relationships, to form an intermediate, and reacting the intermediate with a tin component, which is z1 mols of diorgano tin derivative R1 R2 SnO or R1 R2 SnCl2, or mixture thereof with z2 mols of mono-organo tin derivative which is a stannoic acid monomer or polymer (R1SnO1.5), R1SnCl3,R1Sn(OH)Cl2 or R1Sn(OH)2Cl where R1 and R2 are C1-10 alkyl and x, z1 and z2 have specified interrelationships.

United States Patent Bakassian [75] Inventor: Georges Bakassian, St. FoyLes Lyon, Rhone, France [73] Assignee: Rhone-Poulenc S.A., Paris, France[22] Filed: Dec. 7, 1973 [2]] App]. No.: 423,375

Related US. Application Data [62] Division of Ser. No. 350,122, April11, 1973, Pat.

[30] Foreign Application Priority Data Apr. 12, 1972 France 72.12771Mar. 14. 1973 France 73.09097 [52] US. Cl 260/45.75 S; 260/890 [51] Int.Cl. C08f 45/62 [58] Field of Search 260/45.75 K, 481

[56] References Cited UNITED STATES PATENTS 2.731.484 1/1956 Best260/45.75 3.518.223 6/1970 Fath et a1 1260/4515 Apr. 22, 1975 PrimaryExaminer-V. P. Hoke Attorney, Agent, or FirmSteven, Davis, Miller &Mosher [57] ABSTRACT Unsaturated organo-tin mercaptides, useful asstabilisers for halogenated vinyl resins, are obtained by reacting xmols of a mercaptocarboxylic acid HSXCOOH with y, mols of an alcoholHOYOH or mixture thereof with 2; mols of alcohol HOYOH and/or y mols ofalcohol ROH, where X is C alkylene or phenylene, Y is C alkylene orcycloaliphatic of 5 or 6 ring carbons, each with ethylenic and/oracetylenic bonds but not more than 2 of each type of bonds, Y is Calkylene or cycloalkylene with 5 or 6 ring carbons, R is C alkyl oralkenyl, cycloalkyl or cycloalkenyl with 5 or 6 ring carbons, or phenyl(CH) alkyl, with .r, n; and y having specified inter-relationships, toform an intermediate, and reacting the intermediate with a tincomponent, which is z, mols of diorgano tin derivative R R SnO or R RSnC1 or mixture thereof with 3 mols of mono-organo tin derivative whichis a stannoic acid monomer or polymer (R,SnO, R,SnCl ,R,Sn(OH)Cl orR,Sn(OH) C1 where R and R are C 0 alkyl and x, 1 and 1 have specifiedinterrelationships.

7 Claims, No Drawings UNSATURATED ORGANO-TIN MERCAPTIDE STABlLlZERS FORHALO-VINYL POLYMERS This is a division of application Ser. No. 350,122,filed Apr. 11, 1973 now US. Pat. No. 3,818,062.

This invention relates to organo-tin mercaptides which are particularlysuitable for stabilising chlorinated vinyl resins.

It is known from French Patent Nos. 1,055,906, 1,085,807 and 1,138,451that diorgano-tin mercaptides are good stabilisers for chlorinated vinylresins, and especially for polyvinyl chloride. It has been recommendedto use, in particular, saturated mercaptides such as dibutyl-tin ordioctyl-tin bis-(isooctylmercaptoacetate), these mercaptides currentlyforming the most effective stabilisers. However, these compounds are notcompletely satisfactory in some of their uses. Thus they do not preventthe appearance of a yellow colouration in the manufacture of transparentthin walled objects by high temperature extrusion. It is known that sucha technique of extrusion will give high productivity only if thechlorinated vinyl resin compositions are heated to temperatures of 180to 230C for short periods (e.g. 2 to minutes).

The present invention provides a process for the preparation of anunsaturated organo-tin mercaptide which comprises in step (a) reacting,to form an intermediate x mols of a mercaptocarboxylic acid of theformula:

HS X COOH with a hydroxylic component, which is y, mols of a compound ofthe formula HOYOH or a mixture thereof with at least one of y mols of acompound of formula HO-Y'-OH and y mols of a compound of formula ROH,wherein X represents a straight or branched chain alkylene group of 1 to4 carbon atoms, or a phcnylene group,

Y represents a straight or branched chain, aliphatic,

divalent hydrocarbon radical with at most carbon atoms, or acycloaliphatic radical with 5 or 6 ring carbon atoms, the radical Ybeing divalent with at least one of an ethylenic and acetylenie bond anda maximum of two ethylenic and two acetylenie bonds,

Y represents an alkylene group with 1 to 10 carbon atoms, or acycloalkylene group with 5 or 6 ring carbon atoms, R represents astraight or branched chain alkyl or alkenyl radical with at most 8carbon atoms, a cycloalkyl or cycloalkenyl radical with 5 or 6 ringcarbon atoms, or a phenylalkyl group, the alkyl substituent of whichcontains 1 to 4 carbon atoms, and x,y y and y, are subject to thefollowing inequalities:

yl y and in step (b) reacting the intermediate with a tin component,which is;

Z1 mols of a diorgano-tin derivative of formula R R SnO or R,R SnCl or amixture of 2, mols of the diorgano-tin derivative with Z2 mols of amonoorgano tin derivative, which is a stannoic acid monomer or a polymerthereof with recurring units of formula R,SnO or of formula R,SnClR,Sn(Ol-1)Cl or R Sn(OH) Cl, wherein each of R and R which are the sameor different, represents a straight or branched chain alkyl group with lto 10 carbon atoms, and x, Z] and 22 are subject to the followinginequalities:

The organo-tin mercaptides produced according to the general processwhich has just been defined, have,

a complex structure and can contain in particular the following groups:

Usually the mereaptide contains 1 to 5 of such groups it being possiblein particular for the latter to be bonded in such a way as to formmonomeric, dimeric or oligomeric compounds. By way of illustration, themonomeric and dimeric forms have been represented as follows: i

dimeric form In the process of the invention as unsaturated diol HYOHand a diorgano-tin compound are reacted together. The use of each of thefollowing reagents is optional, a saturated diol, a saturated orunsaturated monoalcohol and a monoorgano-tin derivative, each of theformula given above. Based on the general process, it is thus possibleto define various processes for producing the mercaptides which are ofdifferent degrees of simplicity according to whether only one of the tworeagents, the unsaturated diol or the diorgano-tin derivative, ispartially replaced. The most complex process is that in which all thepossible different variables are involved simultaneously. As is apparentfrom the above inequalities, the replacement of a part of theunsaturated diol is such that the proportion of hydroxyl groups providedby the saturated diol and/or the monoalcohol is at most equal to 50% ofthe overall sum of the hydroxyl groups present in the hydroxyliccomponent. Furthermore, the tin-mercapto-ester group bonds (involvingthe sulphur atom) provided by the monoorgano-tin derivative form at most25% of all the tinmercapto-ester group bonds formed from the diorganotinderivative and the monoorgano-tin derivative.

The compound which results from step (a) of the process, is an unstablecompound which changes easily into a resinous substance. It is thusrecommended not to attempt to isolate it, and to use it rapidly, as itis, for step (b). When y y and Z are 0, and z and y, are 0.5n, then thisintermediate compound comprises in particular the a,w-dimercaptodiesterof the formula:

optionally combined with a small proportion of secondary products of theformula:

It is recommended that the process according to the invention be carriedout in a solvent which is not miscible with water, such for example,aliphatic, cycloaliphatic or aromatic hydrocarbons such as hexane,cyclohexane, petroleum ether, methylcyclohexane, benzene or toluene. Thewater formed during the reaction is advantageously removed e'zg. byazeotropic distillation. In order to assist the esterification reactionof step (a), it is possible to add any known esterification catalyst,for example an acid such p-toluene-sulphonic acid or sulphuric acid. Theconversion into a tin mercaptide is advantageously carried out byemploying a dialkyltin oxide e.g. di-n-butyl or di-n-octyl-tin oxide,preferably with removal of water e.g. by azeotropic distillation. When adichlorodialkylstannane is used, it is preferable simultaneously tointroduce an agent for neutralising the hydrochloric acid liberated(e.g. ammonia or an amine).

Examples of the unsaturated diols, which can be used and whichpreferably have one or two ethylene bonds or one acetylene bond, areZ-butene-l ,4-diol, 2- pentene-l,5-diol, hexene-l,6-diol,octene-l,8-diol, lbutene-3,4-diol, l-pentene-3,4-diol, 2-pentene-l,4diol, 2-hexene- 1,5-diol, 3-heptene-6,7-diol, 4-octene- 3,6-diol,2-butyne-l,4-diol, 2-pentyne-l,4-diol, 3- hexyne-2,5-diol,l,5-hexadiene-3,4-diol, 4-octyne-3,6- diol, 2,6-octadiene-4,5-diol and3-methyl-2,6-heptadiene-4,5-diol. Preferably 2-butene-l,4-diol isadvantageous.

Examples of the mercaptocarboxylic acids are thioglycollic acid,B-mercaptopropionic acid, 'y-mercaptobutyric acid, S-mercaptovalericacid, thiolactic acid, thiosalicylic acid, aand B-mercaptobutyric acidsand B- and 'y-mercaptovaleric acids.

Examples of the saturated or unsaturated monoalcohols are isobutanol,n-butanol, isooctanol, octanol, cyclopentanol, cyclohexanol and phenylethyl alcohol. Preferably isobutanol, n-butanol, isooctanol, octanol areadvantageous.

The unsaturated mercaptides prepared by the process of the invention canbe used, after removal of the solvent, for stabilising halogenated vinylresins and the present invention comprises compositions comprising sucha resin and at least one of the unsaturated mercaptides. They aregenerally introduced into the resin to the extent of 0.2 to 3% by weightrelative to the weight of resin. By halogenated vinyl resins there areto be understood, in accordance with terminology which is well known tothose skilled in the art, polyvinyl chloride and its copolymers in whichthe part originating from vinyl chloride predominates. Examples of thecompounds, which are suitable for copolymerisation with vinyl chloride,are vinyl esters such as vinyl acetate, vinyl bromide, vinyl fluorideand vinyl butyrate, vinyl ethers such as vinyl ethyl ether, acrylic acidand its derivatives such as ethyl acrylate, ethyl methacrylate,acrylonitrile, methacrylonitrile and acrylamide, allyl compounds such asallyl chloride and allyl acetate, and ethylenic compounds such asethylene, propylene and butadiene.

The halogenated vinyl resin may be mixed with other polymers e.g. astyrene/butadiene/methyl methacrylate terpolymer for improving theimpact resistance of the composition.

The mercaptides according to the invention have a greater retardingeffect on yellowing than that of their saturated homologues. Thesemercaptides are thus very particularly suitable for producing thin filmsor transparent objects by extrusion or calendering techniques.

The Examples which follow illustrate the invention.

EXAMPLE 1 44 g of Z-butene-l ,4-diol are introduced slowly, over thecourse of 2 hours 30 minutes, into a flask containing 97 g ofthioglycollic acid, 600 ml of toluene and l g of paratoluenesulphonieacid, the mixture having 5 been brought to the reflux temperature(112C). The water formed is removed completely by azeotropicdistillation. When the esterification is complete, 180 g ofdi-(n-octyl)-tin oxide are added and the mixture is heated under refluxfor 2 hours 15 minutes, with removal of the water formed during thereaction by azeotropic distillation. The toluene is finally removed bydistillation and 235 g of organo-tin mercaptide are obtained, theidentification of which was carried out in EXAMPLE 3 21.5 g of2-butyne-l,4-diol and 250 ml of toluene are introduced into a flask andheated to the reflux temperature (l 10C), and a mixture containing 48 gof thioglycollic acid and 0.5 g of p-toluencsulphonic acid is particularby IR. spectrometry. The product consists Fun in ly e t e COUI'SC f 1hOur. The Water essentially of groups of the formula:

(approximately to determination by infra-red analysis).

[T 11 Sn L 1 C EXAMPLE 2 53 g of B-mercaptopropionic acid and 22 g of 2-butene-l,4-dio1 are reacted, in benzene, in accordance with theprocedure of the preceding Example, and the reaction is continued untilthe water formed has been completely removed. 62 g of di-(n-buty1)-tinoxideare then added and the reaction is continued as in Example 1. 120 gof organo-tin mercaptide consisting essentially of groups of theformula:

(m coo 011 c c cir 000 on formed during the reaction is removed byazeotropic distillation, and then 62 g of dibutyl-tin oxide are addedand the mixture is heated under reflux for minutes, removing the waterformed by azeotropic distillation. After distillation of the toluene,111 g of organo-tin mercaptide, consisting essentially of groups of theformula:

are obtained.

EXAMPLE 4 204 g of thioglycollic acid, 37 g of isobutyl alcohol, 70.5 gof 2-butene-1,4-diol, 1 g of p-toluenesulphonic acid and 1,000 cm ofpetroleum ether are introduced into a flask and heated to the refluxtemperature (57C); the water formed is removed by azeotropic disare thusobtained.

This compound contains small proportions of groups of the formula:

tillation and then 251 g of dibutyl-tin oxide are added and the waterformed is again removed by azeotropic distillation. After removing thesolvent, 491 g of unsat- Sn 000 {0119 s cs cu CH CH2 s (mag coo(approximately 10 to 20%; determination by infra-red analysis).

urated organo-tin mercaptide, consisting essentially of groups of theformula:

Sn-S-CH -COO-CH -0H=Cl'l-Cll -CCO-Cl1 -S and minutes on the calendersand the following samples every 3 minutes thereafter, and thecolourations are 11 C noted (visual examination). The results are givenin the l 3 following table: Sn-S-CH -C0O-CH -CH cn C H 4 9 Duration ofStabilised PVC resin heating at Unsaturated Unsaturated 180C inmercaptide mercaptidc are obtained 10 minutes Example 3 Example 4 5colourless Colourless EXAMPLE 5 8 Colourless Colourless ll ColourlcssColourless Various sample s based on polyvmyl chloride resin, 14cmnurlcss colourless having the following composition, are prepared: 17P1110 yellow Pale yellow 20 Pale yellow Pale yellow Commercial polyvinylchloride, sold commercially l()() g under the tradenamc LUCOVYL BB 800 1l i Styrene/hutadiene/mcthylmethacrylate terpolymer. 10g h h l d used asan additive to increase impact resistance A Compohltlon w K: Comprmc5 aOgcndte 1,3-Butylene glycol ester of oxidised lignite wax, sold 1 gvinyl resin and, 21S stabiliser therefor, 0.2 to 3% by commerciallyunder the tradename Wax E 20 l Stahiliser (diorganotin mcrcaptide) l gWelght of least one un5aturdted o gano-tin mercaptldc prepared by theprocess which comprises in step One of the following stabilisers is usedfor each mixllctmg. to form an intermediate, x mols of a merture;captoearboxyllc acid of the formula:

25 HS-XCOOH .sgflhmscr Thmprcpurcd in Example 1 with a hydroxyliccomponent, which is mols of a Stfibiliser B: 'l'hat prepared in Example2. compound Of the formula HO-YOH O! a mixture Stabiliser C: Preparedaccording to Example 1. i

rcpmcing buwmdinl by Lmhummdm thereof with at least one of y mols of acompound of formula HOY -OH and y mols of a compound of Each mixture ismelted in a two-roll mill, revolving at formula whercm X irepresents aStralght or a speed of 15 revolutions/minute and heated to 180C branchedcham alkylenc group of 1 to 4 carbon atoms (temperature maintained towithin about 2). Samples or phcnylne f Y fcprcsems a Stmlght or areremoved, the first after being worked for 5 minutes branched Cham,allphatlc, dlvalem hydrocarbon Padlon the cakmders and the f ll isamples every 3 cal Wltl'l at most 10 carbon atoms, or a eycloaliphaticminutes thereafter, and the colourations are noted. The radlcal Wlth 5or 6 Carbon atoms, the radical Y examination is carried out with thenaked eye. The yelb61118 dlvalent with at least One Of an hylcnic andlowing numbers are also noted in accordance with the acetylenic bond anda maximum of two ethylenlc and Gardner scale, by means of a Lovibondcomparison (W0 acetylenic bonds, represents an l yl n g oup disc. Theresults are given in the following table: With 1 t0 0 Car n at ms, Or acycloalkylene group Duration of Stabilised PVC resin heating atStabiliser A Stabilizer B Stabilizer C 180C in (Example 1) that ofExample 2 (saturated homologue minutes of stabiliser A) appearanceGARDNER appearance GARDNER appearance GARDNER number number number 5Colourless 0 Colourless 0 Pale yellow 0 8 Colourless 0 Colourless 0Light yellow 1 l l Colourless O Colourless 0 Yellow* 2 l4 Colourless 0Colourless 0 Yellow* 2 l7 Pale yellow 0.5 Pale yellow 0.5 Yellow* 3 20Pale yellow 0.5 Light yellow 0.5 Yellow* 4 increasing intensity Theseexperiments show that the unsaturated orwith 5 or 6 ring-Carbon atoms, Rpf a Straight gano-tin mercaptides have a greater heat stabilising eforbranched Cham alkyl or k y radlcal Wlth at "1 feet than the effectproduced by the saturated homo- 8 Carbon atoms, 11 cycloalkyl orcycloalkenyl radical with 5 or 6 ring carbon atoms, or a phenylalkylgroup, the alkyl substituent of which contains 1 to 4 carbon EXAMPLE 6atoms, and x, y y and y are subject to the following Two stabilisedpolyvinyl chloride resin compositions equa tie are used as in Example 5but with stabilisers A-C re- 2 placed by H 0.8K 2 Y Y 102 1 g of thestabiliser of Example 3 in composition and l g of the stabiliser ofExample 4 in other composix tion. Each mixture is melted in a two-rollmill, revolving at y a speed of 15 revolutions/minute and heated to C. 02 O 25 (temperature maintained to within about 2C). Samplcs are removed,the first after being worked for 5 1 2 and in step (b) reacting theintermediate with a tin component, which is z, mols of a diorgano-tinderivative of formula R R SnO or R R SnCI or a mixture of z, mols of thediorgano-tin derivative with z: mols of a monoorgano-tin derivative,which is a stannoic acid monomer or a polymer thereof with recurringunits of formula R,SnO,, or of formula R,SnCl R,Sn(OH)Cl, or R,Sn(OH)C|, wherein each of R, and R which are the same or different, representsa straight or branched chain alkyl group with l to carbon atoms, and x,Z and 2 are subject to the following inequalities:

oxide.

2. A composition according to claim 1 wherein the halogenated vinylresin is polyvinyl chloride.

3. A composition according to claim 1 which comprises polyvinyl chlorideor a mixture thereof with a styrenc/butadiene/methyl methacrylatetcrpolymer and, as stabiliser therefor, about 1% by weight of anunsaturated organo tin mercaptide prepared by a process which comprisesin step (a) reacting, a mercaptocarboxylic acid, which is thioglycollicor B-mercaptopropionic acid, with a hydroxylic component, which is 2-butyne-l,4-diol, 2-butene-l,4-diol or a mixture of 2- butene-1,4-dioland isobutanol, in the presence of p-toluene-sulphonic acid to form anintermediate, and in step (b) reacting the intermediate with a tin component which is di-(n-butyl) tin oxide or di-(n-octyl) tin 4. Acomposition according to claim 1 wherein z is 5. A composition accordingto claim 1 wherein y is 6. A composition according to claim 1 wherein yis O.

7. A composition according to claim 1 wherein Y contains one ethylenicor acetylenic bond.

1. A COMPOSITION WHICH COMPRISES A HALOGENATD VINYL RESIN AND, ASSTABILISER THEREFOR, 0.2 TO 3% BY WEIGHT OF AT LEAST ONE UNSATURATEDORGANO-TIN MERCAPTIDE PREPARED BY THE PROCESS WHICH COMPRISES IN STEP(A) REACTING, TO FORM AN INTERMEDIATE, X MOLS OF A MERCAPTOCARBOXYLICACID OF THE FORULA:
 1. A composition which comprises a halogenated vinylresin and, as stabiliser therefor, 0.2 to 3% by weight of at least oneunsaturated organo-tin mercaptide prepared by the process whichcomprises in step (a) reacting, to form an intermediate, x mols of amercaptocarboxylic acid of the formula: HS-X-COOH with a hydroxyliccomponent, which is y1 mols of a compound of the formula HO-Y-OH or amixture thereof with at least one of y2 mols of a compound of formulaHO-Y''-OH and y3 mols of a compound of formula ROH, wherein X representsa straight or branched chain alkylene group of 1 to 4 carbon atoms, or aphenylene group, Y represents a straight or branched chain, aliphatic,divalent hydrocarbon radical with at most 10 carbon atoms, or acycloaliphatic radical with 5 or 6 ring carbon atoms, the radical Ybeing divalent with at least one of an ethylenic and acetylenic bond anda maximum of two ethylenic and two acetylenic bonds, Y'' represents analkylene group with 1 to 10 carbon atoms, or a cycloalkylenE group with5 or 6 ring carbon atoms, R represents a straight or branched chainalkyl or alkenyl radical with at most 8 carbon atoms, a cycloalkyl orcycloalkenyl radical with 5 or 6 ring carbon atoms, or a phenylalkylgroup, the alkyl substituent of which contains 1 to 4 carbon atoms, andx, y1, y2 and y3 are subject to the following inequalities:
 2. Acomposition according to claim 1 wherein the halogenated vinyl resin ispolyvinyl chloride.
 3. A composition according to claim 1 whichcomprises polyvinyl chloride or a mixture thereof with astyrene/butadiene/methyl methacrylate terpolymer and, as stabilisertherefor, about 1% by weight of an unsaturated organo tin mercaptideprepared by a process which comprises in step (a) reacting, amercaptocarboxylic acid, which is thioglycollic or Beta-mercaptopropionic acid, with a hydroxylic component, which is2-butyne-1,4-diol, 2-butene-1,4-diol or a mixture of 2-butene-1,4-dioland isobutanol, in the presence of p-toluene-sulphonic acid to form anintermediate, and in step (b) reacting the intermediate with a tincomponent which is di-(n-butyl) tin oxide or di-(n-octyl) tin oxide. 4.A composition according to claim 1 wherein z2 is O.
 5. A compositionaccording to claim 1 wherein y2 is O.
 6. A composition according toclaim 1 wherein y3 is O.